全文获取类型
收费全文 | 2970篇 |
免费 | 122篇 |
国内免费 | 16篇 |
专业分类
化学 | 1820篇 |
晶体学 | 5篇 |
力学 | 129篇 |
数学 | 617篇 |
物理学 | 537篇 |
出版年
2024年 | 3篇 |
2023年 | 33篇 |
2022年 | 91篇 |
2021年 | 127篇 |
2020年 | 73篇 |
2019年 | 91篇 |
2018年 | 68篇 |
2017年 | 52篇 |
2016年 | 115篇 |
2015年 | 110篇 |
2014年 | 125篇 |
2013年 | 191篇 |
2012年 | 226篇 |
2011年 | 249篇 |
2010年 | 146篇 |
2009年 | 109篇 |
2008年 | 202篇 |
2007年 | 172篇 |
2006年 | 160篇 |
2005年 | 164篇 |
2004年 | 114篇 |
2003年 | 105篇 |
2002年 | 94篇 |
2001年 | 38篇 |
2000年 | 31篇 |
1999年 | 25篇 |
1998年 | 15篇 |
1997年 | 28篇 |
1996年 | 21篇 |
1995年 | 17篇 |
1994年 | 16篇 |
1993年 | 13篇 |
1992年 | 6篇 |
1991年 | 2篇 |
1990年 | 8篇 |
1989年 | 7篇 |
1986年 | 4篇 |
1985年 | 6篇 |
1984年 | 7篇 |
1983年 | 8篇 |
1982年 | 3篇 |
1981年 | 5篇 |
1980年 | 5篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 3篇 |
1937年 | 2篇 |
排序方式: 共有3108条查询结果,搜索用时 18 毫秒
171.
Riet Dams Elena Bernabe Anna Nicoletti Claudio Loda Luca Martini Damiano Papini 《Rapid communications in mass spectrometry : RCM》2010,24(17):2650-2654
The introduction of Quality by Design (QbD) in Drug Development has resulted in a greater emphasis on chemical process understanding, in particular on the origin and fate of impurities. Therefore, the identification and quantitation of low level impurities in new Active Pharmaceutical Ingredients (APIs) play a crucial role in project progression and this has created a greater need for sensitive and selective analytical methodology. Consequently, scientists are constantly challenged to look for new applications of traditional analytical techniques. In this context a normal‐phase liquid chromatography/electrospray ionization mass spectrometry (LC/ESI‐MS) method was developed to determine the amount of a de‐fluorinated analogue impurity in Casopitant Mesylate, a new API under development in GlaxoSmithKline, Verona. Normal‐phase LC provided the selectivity needed between our target analyte and Casopitant, while a single quadrupole mass spectrometer was used to ensure the sensitivity needed to detect the impurity at <0.05%w/w. Standard solutions and samples were prepared in heptane/ethanol (50:50, v/v) containing 1% of 2 M NH3 in ethanol; the mobile phase consisted of heptane/ethanol (95:5, v/v) with isocratic elution (flow rate: 1.0 mL/min, total run time: 23 min). To allow the formation of ions in solutions under normal‐phase (apolar) conditions, a post‐column infusion of a solution of 0.1% v/v of formic acid in methanol was applied (flow rate: 200 µL/min). The analysis was carried out in positive ion mode, monitoring the impurity by single ion monitoring (SIM). The method was fully validated and its applicability was demonstrated by the analysis of real‐life samples. This work is an example of the need for selective and accurate methodology during the development of a new chemical entity in order to develop an appropriate control strategy for impurities to ultimately ensure patient safety. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
172.
Mechanical properties of anion exchange membranes by combination of tensile stress–strain tests and dynamic mechanical analysis 下载免费PDF全文
Riccardo Narducci J.‐F. Chailan A. Fahs Luca Pasquini Maria Luisa Di Vona Philippe Knauth 《Journal of Polymer Science.Polymer Physics》2016,54(12):1180-1187
The thermomechanical properties of anion exchange polymers based on polysulfone (PSU) quaternized with trimethylamine (TMA) or 1,4‐diazabicyclo[2.2.2]octane (DABCO) and containing hydroxide or chloride anions by tensile stress–strain tests and dynamic mechanical analysis (DMA) have been determined. The reported mechanical properties included the Young's modulus, tensile strength, and elongation at break from tensile tests and the storage and loss modulus and glass transition temperature from DMA. The anion exchange membranes behaved as stiff polymers with Young's modulus in the order of 1 GPa, relatively with high strength (about 30 MPa) and low elongation at break (around 10%) was observed. Tensile tests were also made with membranes exchanged with hydrogen‐carbonate and carbonate anions to control the absence of important carbonation of the OH form. The glass transition temperatures were of the order of 150 °C (PSU‐TMA) or 200 °C (PSU‐DABCO) for the hydroxide form, confirmed by differential scanning calorimetry; they increase further by about 50 K, when hydroxide ions are replaced by chloride. This result and the increase of the storage modulus could be interpreted by the higher hydration of hydroxide ions and the plasticizing effect of water, which reduced the Van der Waals interactions between the macromolecular chains. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 1180–1187 相似文献
173.
174.
Luca Beverina Dr. 《Chemphyschem》2010,11(10):2075-2077
175.
Zhihui Yi Luca Giacomo Bettini Gaia Tomasello Prajwal Kumar Paolo Piseri Irina Valitova Paolo Milani Francesca Soavi Fabio Cicoira 《Journal of Polymer Science.Polymer Physics》2017,55(1):96-103
Planar organic electrochemical transistors (OECTs) using PEDOT:PSS as the channel material and nanostructured carbon (nsC) as the gate electrode material and poly(sodium 4‐styrenesulfonate (PSSNa) gel as the electrolyte were fabricated on flexible polyethylene terephthalate (Mylar®) substrates. The nsC was deposited at room‐temperature by supersonic cluster beam deposition (SCBD). Interestingly, the OECT acts as a hybrid supercapacitor (to give a device that we indicate as transcap). The energy storage ability of transcaps has been studied with two cell configurations: one featuring PEDOT:PSS as the positive electrode and nsC as the negative electrode and another configuration with reversed electrode polarity. Potentiostatic charge/discharge studies show that both supercapacitors show good performance in terms of voltage retention, in particular, when PEDOT:PSS is used as the positive electrode. Galvanostatic charge–discharge characteristics show typical symmetric triangular shape, indicating a nearly ideal capacitive behavior with a high columbic efficiency (close to 100%). © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 96–103 相似文献
176.
177.
Application of high-resolution magic-angle spinning NMR spectroscopy to define the cell uptake of MRI contrast agents 总被引:1,自引:0,他引:1
Calabi L Alfieri G Biondi L De Miranda M Paleari L Ghelli S 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2002,156(2):222-229
A new method, based on proton high-resolution magic-angle spinning ((1)H HR-MAS) NMR spectroscopy, has been employed to study the cell uptake of magnetic resonance imaging contrast agents (MRI-CAs). The method was tested on human red blood cells (HRBC) and white blood cells (HWBC) by using three gadolinium complexes, widely used in diagnostics, Gd-BOPTA, Gd-DTPA, and Gd-DOTA, and the analogous complexes obtained by replacing Gd(III) with Dy(III), Nd(III), and Tb(III) (i.e., complexes isostructural to the ones of gadolinium but acting as shift agents). The method is based on the evaluation of the magnetic effects, line broadening, or induced lanthanide shift (LIS) caused by these complexes on NMR signals of intra- and extracellular water. Since magnetic effects are directly linked to permeability, this method is direct. In all the tests, these magnetic effects were detected for the extracellular water signal only, providing a direct proof that these complexes are not able to cross the cell membrane. Line broadening effects (i.e., the use of gadolinium complexes) only allow qualitative evaluations. On the contrary, LIS effects can be measured with high precision and they can be related to the concentration of the paramagnetic species in the cellular compartments. This is possible because the HR-MAS technique provides the complete elimination of bulk magnetic susceptibility (BMS) shift and the differentiation of extra- and intracellular water signals. Thus with this method, the rapid quantification of the MRI-CA amount inside and outside the cells is actually feasible. 相似文献
178.
A new approach to solid-state imaging (SSI) is presented. The method relies on narrowing the resonance line using the Lee-Goldburg sequence. The technique is easy to implement in practice and may find widespread applications in materials science. 相似文献
179.
De Luca J 《Chaos (Woodbury, N.Y.)》2005,15(3):33107
We give a Hamiltonian formalism for the delay equations of motion of the electromagnetic two-body problem with arbitrary masses and with either repulsive or attractive interaction. This dynamical system based on action-at-a-distance electrodynamics appeared 100 years ago and it was popularized in the 1940s by the Wheeler and Feynman program to quantize it as a means to overcome the divergencies of perturbative QED. Our finite-dimensional implicit Hamiltonian is closed and involves no series expansions. As an application, the Hamiltonian formalism is used to construct a semiclassical canonical quantization based on the numerical trajectories of the attractive problem. 相似文献
180.
Canevali C Mari CM Mattoni M Morazzoni F Nodari L Ruffo R Russo U Scotti R 《The journal of physical chemistry. B》2005,109(15):7195-7202
The mechanism of NO interaction with nanosized Ru(Pd,Pt)-doped SnO(2) was studied by electron paramagnetic resonance, M?ssbauer, and electric resistance measurements. Three steps were proposed for the reaction between the semiconductor oxide and the gaseous component: (i) the formation of bielectronic oxygen vacancies (V(o)) in SnO(2); (ii) their single-ionization (V(o)(*)) with injection of electrons into the SnO(2) conduction band; (iii) the subsequent transfer of electrons from V(o)(*) to [Ru(Pd,Pt)](4+). The last process induces the formation of further oxygen vacancies which reduce the transition metal centers to lower oxidation states; the redox processes is enhanced and the electrical resistance in transition metal-doped SnO(2) is stronger modified with respect to the undoped material. 相似文献